Ultrafast Vibrational Dynamics and Energy Transfer in Imidazolium Ionic Liquids

Mahesh Namboodiri, Mehdi Mohammad Kazemi, Tahir Zeb Khan, Arnulf Materny, Johannes Kiefer

Research output: Contribution to journalArticle

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Abstract

Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) is used as a probe for monitoring the vibrational dynamics of room temperature ionic liquids (ILs). The experiments are performed on a series of 1,3-dialkylimidazolium ILs containing the bis(trifluoromethylsulfonyl)imide [NTf2] anion. The effect of methylation of the cationic C2 position on the dephasing time is studied analyzing [NTf2]-ILs of 1-ethyl-3-methylimidazohum [EMIM], 1-ethyl-2,3-dimethylimidazolium [EMMIM], 1-butyl-3-methylimidazolium [BMIM], and 1-butyl-2,3-dimethylimidazolium [BMMIM]. Raman coherences are excited around similar to 4400 cm(-1), and the vibrational dephasing of the modes in the fingerprint region is monitored as a function of time. The results indicate that vibrational energy transfer occurs governed by the interionic interactions. This is suggested by mode beating involving vibrations beyond the excitation spectrum as well as systematic differences in the temporal dephasing behavior. In contrast, the length of the cationic alkyl side chain has a negligible impact on the vibrational dynamics.
Original languageEnglish
Pages (from-to)6136-6141
Number of pages6
JournalJournal of the American Chemical Society
Volume136
Issue number16
DOIs
Publication statusPublished - 23 Apr 2014

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Ionic Liquids
Energy Transfer
Ionic liquids
Energy transfer
Imides
Methylation
Anions
Raman Spectrum Analysis
Raman scattering
Dermatoglyphics
Negative ions
Vibration
Monitoring
Temperature
Experiments

Cite this

Namboodiri, M., Kazemi, M. M., Khan, T. Z., Materny, A., & Kiefer, J. (2014). Ultrafast Vibrational Dynamics and Energy Transfer in Imidazolium Ionic Liquids. Journal of the American Chemical Society, 136(16), 6136-6141. https://doi.org/10.1021/ja502527y

Ultrafast Vibrational Dynamics and Energy Transfer in Imidazolium Ionic Liquids. / Namboodiri, Mahesh; Kazemi, Mehdi Mohammad; Khan, Tahir Zeb; Materny, Arnulf; Kiefer, Johannes.

In: Journal of the American Chemical Society, Vol. 136, No. 16, 23.04.2014, p. 6136-6141.

Research output: Contribution to journalArticle

Namboodiri, M, Kazemi, MM, Khan, TZ, Materny, A & Kiefer, J 2014, 'Ultrafast Vibrational Dynamics and Energy Transfer in Imidazolium Ionic Liquids', Journal of the American Chemical Society, vol. 136, no. 16, pp. 6136-6141. https://doi.org/10.1021/ja502527y
Namboodiri, Mahesh ; Kazemi, Mehdi Mohammad ; Khan, Tahir Zeb ; Materny, Arnulf ; Kiefer, Johannes. / Ultrafast Vibrational Dynamics and Energy Transfer in Imidazolium Ionic Liquids. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 16. pp. 6136-6141.
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AB - Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) is used as a probe for monitoring the vibrational dynamics of room temperature ionic liquids (ILs). The experiments are performed on a series of 1,3-dialkylimidazolium ILs containing the bis(trifluoromethylsulfonyl)imide [NTf2] anion. The effect of methylation of the cationic C2 position on the dephasing time is studied analyzing [NTf2]-ILs of 1-ethyl-3-methylimidazohum [EMIM], 1-ethyl-2,3-dimethylimidazolium [EMMIM], 1-butyl-3-methylimidazolium [BMIM], and 1-butyl-2,3-dimethylimidazolium [BMMIM]. Raman coherences are excited around similar to 4400 cm(-1), and the vibrational dephasing of the modes in the fingerprint region is monitored as a function of time. The results indicate that vibrational energy transfer occurs governed by the interionic interactions. This is suggested by mode beating involving vibrations beyond the excitation spectrum as well as systematic differences in the temporal dephasing behavior. In contrast, the length of the cationic alkyl side chain has a negligible impact on the vibrational dynamics.

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